JPH06299363A - Plating method with tin - Google Patents
Plating method with tinInfo
- Publication number
- JPH06299363A JPH06299363A JP5106010A JP10601093A JPH06299363A JP H06299363 A JPH06299363 A JP H06299363A JP 5106010 A JP5106010 A JP 5106010A JP 10601093 A JP10601093 A JP 10601093A JP H06299363 A JPH06299363 A JP H06299363A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- powder
- plated
- plating
- thiourea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、粉末冶金工業等におい
て使用される単一金属粉体への錫めっき方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tin plating method for a single metal powder used in powder metallurgy industry and the like.
【０００２】[0002]
【従来技術】粉体のめっき方法として公知の置換めっき
方法は、めっきしようとする金属を含んだ溶液中で、め
っきしようとする金属より卑な金属粉を還元剤として使
用することにより、目的のめっき金属を析出させること
を反応の基本としている。よって、銅、銀、金等の標準
電極電位が貴な金属を対象とする粉体のめっきの効率、
均一性は良好であるが、それより卑な金属であるニッケ
ル、亜鉛、コバルト、錫の場合においては粉体のめっき
は難しい。2. Description of the Related Art A displacement plating method known as a powder plating method aims at using a metal powder, which is baser than the metal to be plated, as a reducing agent in a solution containing the metal to be plated. The base of the reaction is to deposit the plating metal. Therefore, the efficiency of powder plating for metals with standard electrode potentials such as copper, silver, and gold,
The uniformity is good, but the plating of powder is difficult in the case of the base metals nickel, zinc, cobalt and tin.
【０００３】この対策として、ニッケル、亜鉛、コバル
ト、錫より卑な金属であるアルミニウム、マグネシムを
還元粉と使用してめっきをする方法が提案されている
が、還元率が低いこと、還元粉であるアルミニウム、マ
グネシムの活性が高く扱いにくいこと等の欠点があげら
れる。As a countermeasure against this, there has been proposed a method of plating using aluminum and magnesium, which are base metals less than nickel, zinc, cobalt and tin, with a reducing powder, but the reduction ratio is low and the reducing powder is used. There are drawbacks such as the high activity of certain aluminum and magnesium, which makes them difficult to handle.
【０００４】[0004]
【課題を解決するための手段】本発明者等が単一金属粉
体のめっきについて種々検討した結果、錫より貴な金属
からなる被めっき体と錫を錫イオンを含む水溶液の存在
下で加熱処理することにより、錫を錫より貴な金属をめ
っきできること、及び錫イオンを含む水溶液にチオ尿素
及び／又はチオ尿素誘導体を添加することにより、めっ
きの速度を著しく向上させることができることを見い出
した。Means for Solving the Problems As a result of various studies by the present inventors on plating of a single metal powder, the object to be plated made of a metal nobler than tin and the tin were heated in the presence of an aqueous solution containing tin ions. It has been found that the treatment makes it possible to plate tin with a metal nobler than tin, and that the addition of thiourea and / or a thiourea derivative to an aqueous solution containing tin ions can significantly improve the plating rate. .
【０００５】[0005]
【発明の構成】即ち本発明は、（１）錫より貴な単一金
属からなる被めっき体と錫を錫イオンを含む水溶液の存
在下で加熱処理することを特徴とする錫めっき方法、
（２）錫イオンを含む水溶液にチオ尿素及び／又はチオ
尿素誘導体を添加することを特徴とする前記（１）記載
の錫めっき方法、を提供する。According to the present invention, there is provided (1) a tin plating method, which comprises heat-treating an object to be plated made of a single metal that is noble than tin and tin in the presence of an aqueous solution containing tin ions.
(2) A tin plating method as described in (1) above, wherein thiourea and / or a thiourea derivative is added to an aqueous solution containing tin ions.
【０００６】[0006]
【発明の具体的説明】以下に本発明の理解を容易にする
ため具体的かつ詳細に説明する。本発明のめっきの対象
となる被めっき体は、錫より標準電極電位が貴な金属例
えば銅、銀、金等である。また、金属、無機化合物、高
分子等を予め上記金属で被覆処理したものも包含する。
なお、この被覆処理には、蒸着、無電解メッキ等の公知
の方法が使用される。これらの被めっき体の形状につい
ては特に制限はなく、目的、用途に応じて粉体、線体、
板体等が適宜使用される。以下、被めっき体としては粉
体（以下、単に粉と記載する）を例にとり説明する。DETAILED DESCRIPTION OF THE INVENTION The present invention will be described specifically and in detail below to facilitate understanding. The object to be plated of the present invention is a metal having a standard electrode potential nobler than tin, such as copper, silver or gold. It also includes those obtained by previously coating a metal, an inorganic compound, a polymer or the like with the above metal.
For this coating treatment, known methods such as vapor deposition and electroless plating are used. There is no particular limitation on the shape of these objects to be plated, depending on the purpose and application, powder, wire,
A plate body or the like is used as appropriate. Hereinafter, a powder (hereinafter, simply referred to as a powder) will be described as an example of the object to be plated.
【０００７】本発明でめっき用金属として用いられる錫
の形状は、被めっき粉との接触が可能であればよく、粉
体、板体、線体のいずれでもよいが、被めっき粉と接触
確率を高くとれる粉体（以下、単に粉と記載する）が好
ましい。このときの粉の粒度は、特に制限はないが被め
っき粉の粒度を考慮して決められる。例えば、５０〜１
００μｍの被めっき粉を用いる場合は、篩別等により容
易に被めっき粉とめっき用金属である錫粉を分離できる
粒度の錫粉、すなわち２００μｍ以上のものが適当であ
る。また、錫粉の量は、めっき所要量以上あればよい。The shape of tin used as the metal for plating in the present invention may be any of powder, plate and wire as long as it can contact the powder to be plated. It is preferable to use a powder capable of achieving a high value (hereinafter, simply referred to as a powder). The particle size of the powder at this time is not particularly limited, but is determined in consideration of the particle size of the powder to be plated. For example, 50-1
When using 00 μm of the powder to be plated, tin powder having a particle size that allows the powder to be plated and the tin powder that is the metal for plating to be easily separated by sieving, that is, 200 μm or more is suitable. Moreover, the amount of tin powder should just be more than required plating amount.
【０００８】また、本発明で用いる錫イオンを含む水溶
液としては、塩酸、硫酸もしくは硝酸水溶液であって、
そのｐＨは３以下、好ましくは０．０１〜２のものであ
る。ｐＨが３を超えると錫の水酸化物が生成するため好
ましくない。その使用量は水溶液の錫イオン量がめっき
所要量より過剰になるように調整すればよい。The aqueous solution containing tin ions used in the present invention is an aqueous solution of hydrochloric acid, sulfuric acid or nitric acid.
Its pH is 3 or less, preferably 0.01 to 2. When the pH exceeds 3, tin hydroxide is generated, which is not preferable. The amount used may be adjusted so that the amount of tin ions in the aqueous solution becomes more than the required amount for plating.
【０００９】本発明は上述した被めっき体と錫を錫イオ
ンを含む水溶液の存在下で加熱処理することにより錫め
っきを行うものであるが、その加熱温度は５０〜１００
℃程度でよい。５０℃未満では反応速度が遅く、１００
℃を超えるとコストの面で好ましくない。なお、本めっ
き方法においては被めっき粉とめっき用金属の接触によ
り反応は進むことから、被めっき粉とめっき用金属が繰
り返し接触が続く状態が保たれるよう撹拌することが好
ましい。In the present invention, tin plating is carried out by heating the above-mentioned object to be plated and tin in the presence of an aqueous solution containing tin ions. The heating temperature is 50 to 100.
C may be sufficient. If the temperature is less than 50 ° C, the reaction rate will be slow and 100
If it exceeds ℃, it is not preferable in terms of cost. In the present plating method, the reaction proceeds due to the contact between the powder to be plated and the metal for plating. Therefore, it is preferable to stir the powder to be plated and the metal for plating so as to keep the state of repeated contact.
【００１０】次に本発明の第２の特徴であるチオ尿素及
び／又はチオ尿素誘導体を錫イオンを含有する水溶液に
添加した場合の効果について説明する。チオ尿素及び／
又はチオ尿素誘導体を錫イオンを含有する水溶液に添加
してめっきを行うと、添加しない場合と比較して約４〜
５倍めっき速度が上昇する。この理由については現在の
ところ明確にはわかっていないが、チオ尿素及び／又は
チオ尿素誘導体は錫イオンと錯体を形成しやすいことが
何らかの形でめっき速度を上げることに寄与しているも
のと考えられる。この様にチオ尿素及び／又はチオ尿素
誘導体を添加することにより、生産性が大幅に向上す
る。なお、チオ尿素誘導体としては、ジメチルチオ尿
素、ジエチルチオ尿素、アリルチオ尿素等が例示され
る。その添加の効果が顕著に現われる量は、０．１ｇ／
ｌ以上であり、従って添加量としては、０．１ｇ／ｌ以
上が好ましい。Next, the effect of adding the thiourea and / or the thiourea derivative, which is the second feature of the present invention, to an aqueous solution containing tin ions will be described. Thiourea and /
Alternatively, when a thiourea derivative is added to an aqueous solution containing tin ions and plating is performed, it is about 4 ~
5 times higher plating rate. The reason for this is not clear at present, but it is considered that the thiourea and / or thiourea derivative is likely to form a complex with a tin ion, which contributes to an increase in the plating rate in some way. To be By adding thiourea and / or a thiourea derivative in this way, the productivity is significantly improved. Examples of the thiourea derivative include dimethylthiourea, diethylthiourea, allylthiourea and the like. The amount at which the effect of addition is remarkable is 0.1 g /
Therefore, the amount of addition is preferably 0.1 g / l or more.
【００１１】反応の終了しためっき生成物は、濾過して
液分を除去後、洗浄・防錆・乾燥後篩別して錫めっき粉
体を回収する。濾別されためっき液及び篩別された錫粉
はめっき工程へ循環して再利用される。After the reaction, the plated product is filtered to remove the liquid content, washed, rust-proofed, dried, and then sieved to recover a tin-plated powder. The plating solution filtered out and the tin powder screened out are recycled to the plating step for reuse.
【００１２】[0012]
【実施例】以下、粉末の代表例として、銅を用いた場合
を例にして具体的に説明する。 （実施例１）塩酸でｐＨ０．３に調整した濃度３０ｇ／
ｌの塩化錫水溶液２００ｃｃに銅粉（ＮＣＳ（株）製
＃３４（２０）；１００μｍ以下）１００ｇと錫粉
（０．５ｍｍ以上）５０ｇを入れ撹拌下で７０℃に加熱
し１時間めっきを行った。得られた反応生成物は濾別し
ｐＨ３になるまで純水で洗浄後乾燥した。乾燥した粉末
は、８０ｍｅｓｈの篩いにより被めっき粉とめっき粉と
に分離した。その結果、錫の銀白色を呈した錫めっき粉
が得られた。めっきされた錫量は、１．３ｗｔ％であっ
た。EXAMPLES As a typical example of the powder, a case of using copper will be specifically described below. (Example 1) 30 g / concentration adjusted to pH 0.3 with hydrochloric acid
Copper powder (manufactured by NCS Corporation) in 200 cc of tin chloride aqueous solution
100 g of # 34 (20); 100 μm or less) and 50 g of tin powder (0.5 mm or more) were put and heated to 70 ° C. under stirring for plating for 1 hour. The obtained reaction product was filtered, washed with pure water until pH 3, and dried. The dried powder was separated into a powder to be plated and a plating powder by a 80 mesh sieve. As a result, tin-plated powder showing tin silver color was obtained. The amount of plated tin was 1.3 wt%.
【００１３】（実施例２）塩酸でｐＨ０．３に調整した
濃度３０ｇ／ｌの塩化錫水溶液にチオ尿素１ｇ／ｌを添
加した以外は実施例１と同様にしてめっきを行った。そ
の結果、めっき粉は錫の銀白色を呈した錫めっき粉が得
られた。そのめっきされた量は、５．７ｗｔ％であり、
実施例１のものの約４〜５倍であった。Example 2 Plating was performed in the same manner as in Example 1 except that 1 g / l of thiourea was added to a tin chloride aqueous solution having a concentration of 30 g / l adjusted to pH 0.3 with hydrochloric acid. As a result, a tin-plated powder having a silver-white tin color was obtained. The plated amount is 5.7 wt%,
It was about 4 to 5 times that of Example 1.
【００１４】[0014]
【発明の効果】以上説明したように、本発明により得ら
れる粉末は錫が均一に被覆されており、まためっき液に
チオ尿素及び／又はチオ尿素誘導体を添加することによ
り、生産性が大幅に向上することから、粉末冶金用原料
及び金属粉末の表面処理に好適に用いることができる。As described above, the powder obtained by the present invention is uniformly coated with tin, and the addition of thiourea and / or a thiourea derivative to the plating solution significantly improves the productivity. Since it is improved, it can be suitably used for the surface treatment of powder metallurgy raw materials and metal powders.
Claims (2)
と錫を錫イオンを含む水溶液の存在下で加熱処理するこ
とを特徴とする錫めっき方法。1. A tin plating method, which comprises heat-treating an object to be plated made of a single metal noble than tin and tin in the presence of an aqueous solution containing tin ions.
又はチオ尿素誘導体を添加することを特徴とする請求項
１記載の錫めっき方法。2. An aqueous solution containing tin ions and thiourea and / or
Alternatively, the thiourea derivative is added, and the tin plating method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5106010A JPH06299363A (en) | 1993-04-09 | 1993-04-09 | Plating method with tin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5106010A JPH06299363A (en) | 1993-04-09 | 1993-04-09 | Plating method with tin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06299363A true JPH06299363A (en) | 1994-10-25 |
Family
ID=14422706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5106010A Pending JPH06299363A (en) | 1993-04-09 | 1993-04-09 | Plating method with tin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06299363A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999022894A1 (en) * | 1997-10-30 | 1999-05-14 | Nittetsu Mining Co., Ltd. | Coated powder and process for the preparation thereof |
| WO2005123308A1 (en) * | 2004-06-18 | 2005-12-29 | Mitsui Mining & Smelting Co., Ltd. | Copper-containing tin powder and method for producing the copper-containing tin powder, and electroconductive paste using the copper-containing tin powder |
| JP2006225691A (en) * | 2005-02-15 | 2006-08-31 | Mitsui Mining & Smelting Co Ltd | Tin-coated copper powder and electrically conductive paste using the tin-coated copper powder |
-
1993
- 1993-04-09 JP JP5106010A patent/JPH06299363A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999022894A1 (en) * | 1997-10-30 | 1999-05-14 | Nittetsu Mining Co., Ltd. | Coated powder and process for the preparation thereof |
| US6387532B1 (en) | 1997-10-30 | 2002-05-14 | Nittetsu Mining Co., Ltd. | Coated powder and process for the preparation thereof |
| AU748497B2 (en) * | 1997-10-30 | 2002-06-06 | Katsuto Nakatsuka | Coated powder and process for the preparation thereof |
| CN100444992C (en) * | 1997-10-30 | 2008-12-24 | 日铁矿业株式会社 | Coated powder and process for the preparation thereof |
| WO2005123308A1 (en) * | 2004-06-18 | 2005-12-29 | Mitsui Mining & Smelting Co., Ltd. | Copper-containing tin powder and method for producing the copper-containing tin powder, and electroconductive paste using the copper-containing tin powder |
| JP2006225691A (en) * | 2005-02-15 | 2006-08-31 | Mitsui Mining & Smelting Co Ltd | Tin-coated copper powder and electrically conductive paste using the tin-coated copper powder |
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